Successive Sulfur Oxidation Directs Topological Transformation From 4₁ Knot to 6 3 2 $6_3^2$ Link

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Chemical Synthesis

Background:

• Achieving controlled topological transformations in supramolecular chemistry is challenging.
• Sulfur-containing molecules offer potential for stimuli-responsive behavior.

Purpose of the Study:

• To develop a novel method for triggering topological transformations in metallosupramolecular cages.
• To investigate the use of sulfur oxidation as a stimulus for interconverting molecular topologies.

Main Methods:

• Synthesis of a thioether-type octanuclear metallic knot (M) via self-assembly.
• Stepwise oxidation of sulfur centers (-S- to -S(O)- to -S(O)2-) to induce topological changes.
• Characterization of intermediate and final products using analytical techniques.

Main Results:

• Successfully transformed the octanuclear knot (M) into a dodecanuclear link (M-O) and subsequently to another link (M-2O).
• Demonstrated a dual increase in metal nuclearity and crossing complexity during the transformation.
• Showcased precise control over molecular geometry and topology via stepwise sulfur oxidation.

Conclusions:

• Established a novel oxidation-mediated interconversion paradigm for complex molecular topologies.
• Highlighted the potential of embedded sulfur centers as molecular triggers for dynamic systems.
• Provided insights for designing advanced intelligent material systems with tunable properties.